Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
  • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
  • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings

Definitions

• the yields obtained are from 75 to 82% of theory.
• the Patent further discloses that at least 5 parts of copper sulfate or copper acetate are required, per 100 parts of ⁇ -hydroxyacetylene, in order to achieve this result.
• N-disubstituted 1-aminoalk-2-yn-4-ols of the above formula I may be obtained in better yield, and with less catalyst, than hitherto, by reacting an alkynol with formaldehyde and a secondary amine in acid aqueous solution in the presence of a copper compound, if the reaction is carried out in the presence of a bromide or iodide which is soluble in the reaction mixture, or in the presence of iodine.
• 1-Dialkylaminoalk-2-yn-4-ols are valuable intermediates for the manufacture of crop protection agents and drugs.
• the reaction of the amine, aqueous formaldehyde and ⁇ -hydroxyacetylene is generally carried out at a pH of from 2 to 7, preferably of about 5, and preferably in the presence of a mineral acid.
• the bromides or iodides which are soluble in the reaction mixture may be, for example, the alkali metal salts of hydriodic acid or hydrobromic acid or, at least partly, the hydrohalic acids. Of course, they may also be used as a mixture.
• the copper compound employed is advantageously a chloride, nitrate or acetate, but preferably the sulfate, i.e. a Cu(II) compound soluble in the reaction mixture.
• the direct use of copper-I iodide appears to be less effective, possibly due to the fact that this compound is only sparingly soluble in the reaction mixture. This situation was not to be deduced from the known investigations in this field, e.g.
• radicals R 1 and R 4 may be hydrogen or aliphatic or aromatic hydrocarbon radicals having e.g. from 1 to 10 carbon atoms.
• the reaction in general does not depend on the nature of these radicals, unless they exhibit substituents which are known to the skilled worker to prevent or change the reaction under consideration.
• Examples of compounds (I) that may be manufactured according to the invention are mono- and dimethylamino, mono- and diethylamino, methylbutylamino, methylisoprenylamino, phenylamino and decylamino derivatives of appropriate propynols, butynols, pentynols or decynols, the alkynols being straight-chain or branched.
• the reaction may be carried out at a satisfactory rate at from about 65° C. to the boiling point of the mixture, preferably from 85° to 95° C. In principle, it is also possible to select a different temperature, given appropriate conditions.
• the resulting salts of the dialkylaminoalkynols with mineral acids may be saponified with alkali or ammonia and worked up in the conventional manner. Experience shows the yield to be from 85 to more than 90% of theory.
• 204 parts by weight of aqueous 55% strength propargyl alcohol, 250 parts by weight of 30% strength aqueous formaldehyde, 161 parts by weight of diethylamine, 1.4 parts by weight of copper sulfate, 2 parts by weight of potassium iodide, 50 parts by weight of water and 115 parts by weight of concentrated sulfuric acid are mixed and brought to pH 5.
• the mixture is heated for 5 hours at 92° C. and worked up as described. 242 parts by weight of 1-diethylaminobut-2-yn-4-ol are obtained, corresponding to a yield of 86%.
• Example 1 The procedure followed is as described in Example 1. Instead of 1.3 parts by weight, 2.3 parts by weight of copper sulfate are used, and instead of 2 parts by weight of potassium iodide, 2.3 parts by weight of potassium bromide are used. After working up, 270 parts by weight of 1-diethylaminopent-2-yn-4-ol are obtained, corresponding to a yield of 87.2%.
• Example 2 The procedure described in Example 2 is followed. Instead of 2 parts by weight of potassium iodide, 2 parts by weight of sodium iodide are employed. 244 parts by weight of 1-diethylaminobut-1-yn-4-ol are obtained, corresponding to a yield of 87%.
• Example 1 The procedure described in Example 1 is followed. Instead of 1.3 parts by weight, 2.3 parts by weight of copper sulfate are employed, and instead of 2 parts by weight of potassium iodide, 2.5 parts by weight of sodium bromide are employed. The reaction is carried out at 85° C. 268 parts by weight of 1-diethylaminopent-2-yn-4-ol are obtained, corresponding to a yield of 86%.
• Example 2 The procedure described in Example 1 is followed. Instead of diethylamine, 142 parts by weight of pyrrolidine are employed. 280 parts by weight of 1-pyrrolidinopent-2-yn-4-ol are obtained, corresponding to a yield of 91%.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Cited By (3)

Citations (2)

• 1976
  • 1976-08-20 DE DE2637425A patent/DE2637425C3/de not_active Expired
• 1977
  • 1977-08-11 FR FR7724722A patent/FR2362113A1/fr active Granted
  • 1977-08-15 US US05/824,523 patent/US4148824A/en not_active Expired - Lifetime
  • 1977-08-19 GB GB34870/77A patent/GB1581781A/en not_active Expired
  • 1977-08-19 HU HU77BA3573A patent/HU177936B/hu unknown

Patent Citations (2)

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